Abstract

Tin (Sn) anode active particles were electrochemically lithiated during simultaneous imaging in a scanning electron microscope. Relationships among the reaction mechanism, active particle local strain rate, particle size, and microcrack formation are elucidated to demonstrate the importance of strain relaxation due to mechano-electrochemical interaction in Sn-based electrodes under electrochemical cycling. At low rates of operation, due to significant creep relaxation, large Sn active particles, of size 1 μm, exhibit no significant surface crack formation. Microcrack formation within Sn active particles occurs due to two different mechanisms: (i)large concentration gradient induced stress at the two-phase interface, and (ii) high volume expansion induced stress at the surface of the active particles. From the present study, it can be concluded that majority of the microcracks evolve at or near the particle surface due to high volume expansion induced tension. Concentration gradient induced damage prevails near the center of the active particle, though significantly smaller in magnitude. Comparison with experimental results indicates that at operating conditions of C/2, even 500 nm sized Sn active particles remain free from surface crack formation, which emphasizes the importance of creep relaxation. A phase map has been developed to demonstrate the preferred mechano-electrochemical window of operation of Sn-basedmore » electrodes.« less

Tin (Sn) anode active particles were electrochemically lithiated during simultaneous imaging in a scanning electron microscope. Relationships among the reaction mechanism, active particle local strain rate, particle size, and microcrack formation are elucidated to demonstrate the importance of strain relaxation due to mechano-electrochemical interaction in Sn-based electrodes under electrochemical cycling. At low rates of operation, due to significant creep relaxation, large Sn active particles, of size 1 μm, exhibit no significant surface crack formation. Microcrack formation within Sn active particles occurs due to two different mechanisms: (i)large concentration gradient induced stress at the two-phase interface, and (ii) high volume expansionmore » induced stress at the surface of the active particles. From the present study, it can be concluded that majority of the microcracks evolve at or near the particle surface due to high volume expansion induced tension. Concentration gradient induced damage prevails near the center of the active particle, though significantly smaller in magnitude. Comparison with experimental results indicates that at operating conditions of C/2, even 500 nm sized Sn active particles remain free from surface crack formation, which emphasizes the importance of creep relaxation. A phase map has been developed to demonstrate the preferred mechano-electrochemical window of operation of Sn-based electrodes.« less

High-capacity anode materials for lithium-ion batteries, such as silicon, are prone to large volume change during lithiation/delithiation which may cause particle cracking and disintegration, thereby resulting in severe capacity fade and reduction in cycle life. In this work, a stochastic analysis is presented in order to understand the mechano-electrochemical interaction in silicon active particles along with a surface film during cycling. Amorphous silicon particles exhibiting single-phase lithiation incur lower amount of cracking as compared to crystalline silicon particles exhibiting two-phase lithiation for the same degree of volumetric expansion. Rupture of the brittle surface film is observed for both amorphous andmore » crystalline silicon particles and is attributed to the large volumetric expansion of the silicon active particle with lithiation. The mechanical property of the surface film plays an important role in determining the amount of degradation in the particle/film assembly. A strategy to ameliorate particle cracking in silicon active particles is proposed.« less

Electrochemical strains are a ubiquitous feature of solid state ionic devices ranging from ion batteries and fuel cells to electroresistive and memristive memories. We proposed a scanning probe microscopy (SPM) based approach, referred as electrochemical strain microscopy (ESM), for probing local ionic flows and electrochemical reactions in solids based on bias-strain coupling. In ESM, the sharp SPM tip concentrates the electric field in a small (10-50 nm) region of material, inducing interfacial electrochemical processes and ionic flows. Furthermore, we use the resultant electrochemical strains to determine it from dynamic surface displacement and provide information on local electrochemical functionality. We alsomore » analyze image formation mechanism in ESM for a special case of mixed electronic-ionic conductor with blocking tip electrode, and determine frequency dependence of response, role of diffusion and electromigration effects, and resolution and detection limits.« less

Virtually all intercalation compounds used as battery electrodes exhibit significant changes in unit cell volume during use. Na xFePO 4 (0 < x < 1, NFP) olivine, of interest as a cathode for sodium-ion batteries, is a model for topotactic, high strain systems as it exhibits one of the largest discontinuous volume changes (~17% by volume) during its first-order transition between two otherwise isostructural phases. Using synchrotron radiation powder X-ray diffraction (PXD) and pair distribution function (PDF) analysis, we discover a new strain-accommodation mechanism wherein a third, <10 nm scale nanocrystalline phase forms to buffer the large lattice mismatch betweenmore » primary phases. The new phase has a and b lattice parameters matching one crystalline endmember phase and c lattice parameter matching the other, and is not detectable by powder diffraction alone. Finally, we suggest that this strain-accommodation mechanism may apply to systems with large transformation strains but in which true “amorphization” does not occur.« less

Here, lithium manganate Li xMn 2O 4 (LMO) is a lithium ion cathode that suffers from the widely observed but poorly understood phenomenon of capacity loss due to Mn dissolution during electrochemical cycling. Here, operando X-ray reflectivity (low- and high-angle) is used to study the structure and morphology of epitaxial LMO (111) thin film cathodes undergoing lithium insertion and extraction to understand the inter-relationships between biaxial strain and Mn-dissolution. The initially strain-relieved LiMn 2O 4 films generate in-plane tensile and compressive strains for delithiated (x < 1) and overlithiated (x > 1) charge states, respectively. The results reveal reversible Limore » insertion into LMO with no measurable Mn-loss for 0 < x < 1, as expected. In contrast, deeper discharge (x > 1) reveals Mn loss from LMO along with dramatic changes in the intensity of the (111) Bragg peak that cannot be explained by Li stoichiometry. These results reveal a partially reversible site reorganization of Mn ions ithin the LMO film that is not seen in bulk reactions and indicates a transition in Mn-layer toichiometry from 3:1 to 2:2 in alternating cation planes. Density functional theory calculations confirm that compressive strains (at x = 2) stabilize LMO structures with 2:2 Mn site distributions, therefore providing new insights into the role of lattice strain in the stability of LMO.« less